CN1831071B - Anti-dazzle hardness film coating - Google Patents
Anti-dazzle hardness film coating Download PDFInfo
- Publication number
- CN1831071B CN1831071B CN2006100074640A CN200610007464A CN1831071B CN 1831071 B CN1831071 B CN 1831071B CN 2006100074640 A CN2006100074640 A CN 2006100074640A CN 200610007464 A CN200610007464 A CN 200610007464A CN 1831071 B CN1831071 B CN 1831071B
- Authority
- CN
- China
- Prior art keywords
- silica granule
- hard coat
- film
- size
- dazzle
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZBVQEUUTPTVMHY-UHFFFAOYSA-N phenyl-(2-phenylphenyl)methanone Chemical compound C=1C=CC=C(C=2C=CC=CC=2)C=1C(=O)C1=CC=CC=C1 ZBVQEUUTPTVMHY-UHFFFAOYSA-N 0.000 description 1
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 230000003405 preventing effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
- F21V35/00—Candle holders
- F21V35/006—Drop catchers; Shade holders
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C5/00—Candles
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Surface Treatment Of Optical Elements (AREA)
- Paints Or Removers (AREA)
- Optical Elements Other Than Lenses (AREA)
Abstract
One kind of hard antidazzle coating is provided, which has excellent antidazzle property, good visibility, high surface hardness and no degradation of high precision display quality and is suitable for use as the surface protecting coating for various kinds of display screen. The antidazzle coating is formed with activation energy cured resin composition containing silica grains, and the silica grains in the composition has grain size distribution with peaks in 0.1-1 micron and 1.5-5 micron and average grain size of 4 micron or below and content of 1-20 wt% of the solid components in the composition.
Description
Technical field
The present invention relates to anti-dazzle hardness film coating.More particularly; relate to a kind of anti-dazzle hardness film coating; it can not reduce high-accuracy demonstration image quality; can give good anti-dazzle property; be used for various indicating meters for example liquid-crystal display (LCD), plasma display (PDP), cathode ray tube (CRT) and when using visual good (expression sharpness height) as touch panel etc.; can increase surface hardness, be suitable as surface protection film.
Background technology
In the display screen of CRT and liquid crystal display etc., light is injected from the picture outside, this luminous reflectance (being called as dazzle or thorn sight (ギ ラ Star キ) etc.), the situation that appearance is difficult to see display image, particularly in recent years, along with the maximization of display screen, addressing the above problem becomes more and more important problem.
In order to address this is that, so far various display screens various non-glare treated have been carried out.As one of them, for example in liquid crystal display, the hard coat film that uses in the polaroid and the protection of various display screen are carried out the non-glare treated of surface roughening with hard coat film etc.The anti-dazzle processing method of this hard coat film can be divided into (1) usually and adopt physical method to carry out the method two big classes that the method for surface roughening and (2) are forming mixed fillers in the hard paint that hard coat uses when the curing that forms hard coat.
In these two kinds of methods, the method for latter's mixed fillers in hard paint is a main stream approach, and, as filler, mainly use silica granule.As the reason of using silica granule, can enumerate the whiteness that can suppress the gained hard coat film and descend, and favorable dispersity etc. can not reduce hardness, and sneak into paint the time.
But,,,,, also can produce the unavoidable problem that descends of its image quality even then the liquid crystal display knuckle is high-accuracy if use in the past non-high-accuracy hard coat film (feeling coarse) as above-mentioned anti-dazzle hardness film coating for example when liquid crystal display when being high-accuracy.Therefore, in order to obtain the high image quality that high-accuracy liquid crystal display possesses, high-accuracy anti-dazzle hardness film coating must be arranged.
In the former anti-dazzle hardness film coating, using median size usually is silica granule about 1～2.5 μ m.The anti-dazzle property of this silica granule is good, but can not adapt in recent years high-accuracyization liquid crystal display etc., and makes it show image quality reduction.
Practical situation are, in the anti-dazzle hardness film coating of silica granule that this independent use median size is 1～2.5 μ m, also do not find can not make the image quality reduction of high-accuracyization liquid crystal display in recent years and can give the hard coat film of good anti-dazzle property as filler.
Therefore, attempted making the method (referring to for example patent documentation 1) that contains colloided silica particle aggregation thing in the hard coat, made combination in the hard coat contain atomic method (referring to for example patent documentation 2) that silica granule that median size is 0.5～5 μ m and median size be 1～60nm etc., but need further promote clearness.
In addition, disclose also on transparency carrier that to form by specific refractory power be the scuff resistance anti-dazzle film (referring to for example patent documentation 3) that antiglare layer that 1.40～1.60 resin beads and ionizing ray curable resin composition constitute forms.In this anti-dazzle film, as preferred resin beads, using particle diameter is polymethylmethacrylate bead, polycarbonate pellets, polystyrene sphere, polypropylene vinylbenzene bead, the polyvinyl chloride bead of 3～8 mu m ranges, and, in order to prevent the sedimentation in paint of these resin balls, in per 100 weight part ionizing ray curable resins, the particle diameter that adds about less than 0.1 weight part is 0.5 μ m or following silica bead.
Like this, in above-mentioned communique,, in antiglare layer, disperseed the relatively large typical resin beads of particle diameter, but the not necessarily enough good problem of scuff resistance of antiglare layer occurred in order to give anti-dazzle property.
[patent documentation 1] spy opens flat 10-180950 communique
[patent documentation 2] spy opens the 2002-36452 communique
[patent documentation 3] spy opens flat 6-18706 communique
Summary of the invention
The present invention is based on above-mentioned situation, purpose provides a kind of anti-dazzle hardness film coating, and it can not make high-accuracy demonstration image quality reduction, can give good anti-dazzle property, and is visual good when being used for various display screen, and surface hardness is big, is suitable as surface protection film.
Present inventors are the above-mentioned anti-dazzle hardness film coating with premium properties of exploitation, specialize in repeatedly, found that, by use contain in the size-grade distribution of measuring by laser diffraction and scattering method particle diameter in certain two scope, have respectively peak value, median size is that the active energy ray-curable resin combination of 4 μ m or following silica granule forms hard coat film, can realize this purpose, based on this discovery, finished the present invention.
That is to say, the invention provides:
(1) a kind of anti-dazzle hardness film coating, it is characterized in that on the one side at least of base material film, having by employing and contain the hard coat that cured article that the active energy ray-curable resin combination of silica granule forms forms, and the silica granule in the above-mentioned composition has peak value respectively for particle diameter in the size-grade distribution of being measured by the laser diffraction and scattering method in the scope of 0.1～1 μ m and 1.5～5 μ m and median size is 4 μ m or following silica granule, the content of this silica granule is 1～20 weight % based on the solids component weight of above-mentioned composition;
(2) a kind of anti-dazzle hardness film coating, the expression sharpness that it is characterized in that (1) described anti-dazzle hardness film coating have 100 or above value;
(3) above-mentioned (1) or (2) described anti-dazzle hardness film coating, wherein contain by particle diameter in the size-grade distribution of laser diffraction and scattering method mensuration and in the scope of 0.1～1 μ m and 1.5～5 μ m, have peak value respectively, and median size is the active energy ray-curable resin combination of 4 μ m or following silica granule, bigger by containing than above-mentioned silica granule median size, and the active energy ray-curable resin combination that has the silica granule of 1 peak value in the size-grade distribution of being measured by the laser diffraction and scattering method carries out grinding dispersion treatment by the machine with grinding dispersion function that utilizes shearing force, the median size that makes silica granule than grinding dispersion treatment before little 0.5 μ m or above and make;
(4) above-mentioned (1), (2) or (3) described anti-dazzle hardness film coating, wherein the arithmetic average roughness Ra of hard coat is 0.05～0.15 μ m; With
(5) above-mentioned (1)～(4) any described anti-dazzle hardness film coating, wherein the thickness of hard coat is 0.5～20 μ m.
According to the present invention, a kind of anti-dazzle hardness film coating can be provided, it can not make high-accuracy demonstration image quality reduction; can give good anti-dazzle property; when being used for various display screen visual good (expression sharpness height), and surface hardness is big, is suitable as surface protection film.
Description of drawings
Fig. 1 is the particle size distribution figure of silica granule in the active energy ray-curable resin combination among the demonstration embodiment 1.
Fig. 2 is the particle size distribution figure of silica granule in the active energy ray-curable resin combination among the demonstration embodiment 2.
Fig. 3 is the particle size distribution figure of silica granule in the active energy ray-curable resin combination among the demonstration embodiment 3.
Fig. 4 is the particle size distribution figure of silica granule in the active energy ray-curable resin combination among the demonstration embodiment 4.
Fig. 5 is the particle size distribution figure of silica granule in the active energy ray-curable resin combination in the demonstration comparative example 1.
Fig. 6 is the particle size distribution figure of silica granule in the active energy ray-curable resin combination in the demonstration comparative example 2.
Fig. 7 is the particle size distribution figure of silica granule in the active energy ray-curable resin combination in the demonstration comparative example 3.
Fig. 8 is the particle size distribution figure of silica granule in the active energy ray-curable resin combination in the demonstration comparative example 4.
Embodiment
In the anti-dazzle hardness film coating of the present invention base material is had no particular limits, can be from using with suitable selection the known plastics film of hard coat film base material as optics in the past.As this plastics film, can enumerate for example polyethylene terephthalate, polybutylene terephthalate, polyester films such as poly-naphthalene ethyl ester, polyethylene film, polypropylene film, cellulose film, the diacetyl cellulose film, triacetylcellulose film, cellulose acetate butyric ester film, polyvinyl chloride film, polyvinylidene chloride film, PVA (PVOH) FILM, the ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, poly-methyl pentene film, polysulphone film, poly (ether ether ketone) film, the polyethersulfone film, the polyetherimide film, Kapton, the fluorine-type resin film, polyamide layer, the acrylic resin film, the norbornene resin film, cyclic olefin resins film etc.
These base material films are transparent, translucent all passable, and, also can be painted, also can be colourless, purposes is suitably selected to get final product as required.For example when the protection time spent as liquid crystal display, water white film is more suitable.
Thickness to these base material films has no particular limits, and can according to circumstances suitably select, and is generally 15～300 μ m, is preferably the scope of 30～200 μ m.In addition, this base material film can be implemented surface treatment by oxidation style or concavo-convexization method etc. to its one side or two sides as required for improving the binding property purpose that goes up the layer that is provided with its surface.As above-mentioned oxidation style, can enumerate for example Corona discharge Treatment, chromic acid processing (wet method), flame treating, hot blast processing, ozone uviolizing processing etc., in addition,, can enumerate for example sand-blast, solvent treatment method etc. as concavo-convexization method.These surface preparations can suitably be selected according to the kind of base material film, usually, consider from effect and operability equal angles, preferably use the Corona discharge Treatment method.
Anti-dazzle hardness film coating of the present invention has the hard coat that cured article that the active energy ray-curable resin combination that contains silica granule by employing forms constitutes on the one side at least of above-mentioned base material film.
Above-mentioned active energy ray-curable resin combination is the composition that contains active energy ray-curable polymerizable compound, silica granule and Photoepolymerizationinitiater initiater as required and other various added ingredientss etc.
In addition, the active energy ray-curable polymerizable compound is meant that the ray that has an energy quantum by irradiation hertzian wave or this inside of charged particle ray is ultraviolet ray or electron beam, can produce crosslinked, solidified polymerizable compound.
As this active energy ray-curable polymerizable compound, can enumerate for example activation-energy-ray polymerizability prepolymer and/or activation-energy-ray polymerizable monomer.Above-mentioned activation-energy-ray polymerizability prepolymer comprises radical polymerization mould assembly and cationic polymerization type, as radical polymerization mould assembly activation-energy-ray polymerizability prepolymer, can enumerate for example polyester acrylate class, epoxy acrylate class, urethane acrylate class, polyalcohol acrylate class etc.
Here, as polyester acrylate class prepolymer, can carry out esterification with (methyl) vinylformic acid by the hydroxyl that for example will have the polyester oligomer of hydroxyl, perhaps will carry out esterification with (methyl) vinylformic acid and obtain by the terminal hydroxyl of the oligopolymer of polycarboxylic acid addition oxirane gained by two ends of polycarboxylic acid and polyol condensating gained.The bisphenol-type epoxy resin that epoxy acrylate class prepolymer can be by for example making relatively low molecular weight or the oxyethane ring of phenol aldehyde type epoxy resin carry out esterification with the reaction of (methyl) vinylformic acid and obtain.Urethane acrylate class prepolymer can carry out esterification with (methyl) vinylformic acid by the urethane oligomer that for example will be obtained by the reaction of polyether glycol or polyester polyol and polymeric polyisocyanate and make.In addition, polyalcohol acrylate class prepolymer can carry out esterification with (methyl) vinylformic acid by the hydroxyl with polyether glycol and makes.These activation-energy-ray polymerizability prepolymers can use a kind, also can 2 kinds or above being used in combination.
On the other hand, as cationic polymerization type activation-energy-ray polymerizability prepolymer, use redix usually.As this redix, for example can enumerate with polyatomic phenols such as bisphenol resin or resol with epoxidised compounds such as epoxy chloropropane, with straight chain shape olefin(e) compound or cyclic olefin compound with compound of oxidation gained such as superoxide etc.
In addition, as the activation-energy-ray polymerizable monomer, can enumerate 1,4-butyleneglycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, NPGA neopentyl glycol adipate two (methyl) acrylate, hydroxypivalic acid neopentyl glycol two (methyl) acrylate, two pentamethylene base two (methyl) acrylate, caprolactone modification dicyclopentenyl two (methyl) acrylate, oxyethane modified phosphate two (methyl) acrylate, allylation cyclohexyl two (methyl) acrylate, isocyanuric acid ester two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, Dipentaerythritol three (methyl) acrylate, Dipentaerythritol three (methyl) acrylate of propionic acid modification, tetramethylolmethane three (methyl) acrylate, the trimethylolpropane tris of epoxy pronane modification (methyl) acrylate, three (acryloxy ethyl) isocyanuric acid ester, Dipentaerythritol five (methyl) acrylate of propionic acid modification, Dipentaerythritol six (methyl) acrylate, multi-functional acrylates such as Dipentaerythritol six (methyl) acrylate of caprolactone modification.These activation-energy-ray polymerizable monomers can use a kind, also can 2 kinds or above being used in combination, and, can also with the coupling of above-mentioned activation-energy-ray polymerizability prepolymer.
In addition, as the Photoepolymerizationinitiater initiater that uses as required, optical polymerism prepolymer or photopolymerization monomer for the radical polymerization mould assembly in activation-energy-ray polymerizability prepolymer or the monomer, can enumerate for example bitter almond oil camphor, benzoin methylether, ethoxybenzoin, benzoin iso-propylether, benzoin n-butylether, the bitter almond oil camphor ethyl isobutyl ether, methyl phenyl ketone, the dimethylamino methyl phenyl ketone, 2,2-dimethoxy-2-phenyl methyl phenyl ketone, 2,2-diethoxy-2-phenyl methyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, the 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholine-propane-1-ketone, 4-(2-hydroxyl-oxethyl) phenyl-2-(hydroxyl-2-propyl group) ketone, benzophenone, to the phenyl benzophenone, 4,4 '-diethylamino benzophenone, two chloro benzophenones, 2-methylanthraquinone, 2-ethyl-anthraquinone, 2-tertiary butyl anthraquinone, the 2-aminoanthraquinone, 2-methylthio group xanthone, 2-ethylmercapto group xanthone, 2-chlorine sulphur xanthone, 2,4-diformazan sulfenyl xanthone, 2,4-diethyl sulfenyl xanthone, benzyl dimethyl ketal, the methyl phenyl ketone dimethyl ketal, right-dimethylamino benzoate etc.In addition, for cationic polymerization type optical polymerism prepolymer, as Photoepolymerizationinitiater initiater, can enumerate for example compound of negatively charged ion compositions such as aromatic matte ion, aromatic series oxygen sulfonium cation, aromatic series iodide ion plasma and a tetrafluoro borate, hexafluorophosphate, hexafluoro antimonate, hexafluoro arsenate.They can use a kind, also can 2 kinds or above being used in combination, and in addition, its combined amount is selected in the scope of 0.2～10 weight part usually with respect to above-mentioned optical polymerism prepolymer of 100 weight parts and/or photopolymerization monomer.
In the present invention, as silica granule contained in the active energy ray-curable resin combination, particle diameter is at 0.1～1 μ m, preferred 0.2～1 μ m, more preferably have peak value respectively in the scope of 0.3～1 μ m and 1.5～5 μ m in the size-grade distribution of being measured by the laser diffraction and scattering method in use, and median size is 4 μ m or following silica granule.
Silica granule by use has this size-grade distribution and median size can not make high-accuracy demonstration image quality reduction, can give good anti-dazzle property, and visuality become well (the expression sharpness increases) when being used for various display screen.As median size, be generally 0.3～4 μ m, be preferably 0.5～3 μ m.
The active energy ray-curable resin combination that contains silica granule with above-mentioned size-grade distribution and median size, can carry out grinding dispersion treatment by the machine that utilizes shearing force by for example containing the active energy ray-curable resin combination that has the silica granule at 1 peak than purpose silica granule median size in the big and size-grade distribution that measure by the laser diffraction and scattering method with grinding dispersion function, the median size that makes silica granule than grinding dispersion treatment before little 0.5 μ m or above and make.
As above-mentioned utilize shearing force have a grinding dispersion function machine, can use machine, for example roll-type milling machine, ball mill (beads mill), aeropulverizer etc. with high shear force.
By carrying out grinding dispersion treatment, make silica granule have above-mentioned size-grade distribution and median size with this machine with high shear force.The specific surface area of being measured by the laser diffraction and scattering method of this silica granule is generally 20000cm
2/ cm
3Or more than.
In addition, for the laser diffraction and scattering method, will in aftermentioned, describe.
The silica granule that uses among the present invention can be with organic surface treatment agent processing have been carried out on the surface, also can be untreated.As above-mentioned organic surface treatment agent, can use silicane coupler or silicone oil, silicone wax etc.
As above-mentioned silicane coupler, can enumerate for example triethoxyl silane, vinyl three ('beta '-methoxy oxyethyl group) silane, γ-methacryloxypropyl trimethoxy silane, γ-glycidoxypropyltrime,hoxysilane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, N-β-(amino-ethyl)-gamma-amino propyl trimethoxy silicane, N-β-(amino-ethyl)-gamma-amino propyl group methyl dimethoxysilane, γ-An Jibingjisanyiyangjiguiwan, N-phenyl-gamma-amino propyl trimethoxy silicane, γ-Qiu Jibingjisanjiayangjiguiwan, γ-r-chloropropyl trimethoxyl silane etc.Preferred γ-An Jibingjisanyiyangjiguiwan, N-β-aminosilane classes such as (amino-ethyl)-gamma-amino propyl trimethoxy silicane in the middle of them.
The method of handling this silica granule with above-mentioned surface treatment agent is had no particular limits, so long as former customary way, for example aqua-solution method, organic solvent method, spraying are gone etc., then can use arbitrary method.
The content of the above-mentioned silica granule in the active energy ray-curable resin combination, based on solids component weight, selected in the scope of 1～20 weight %.If the content of this silica granule be 1 weight % or more than, then can bring into play and give the effect of hard coat with good anti-dazzle property, and if 20 weight % or following, the scuff resistance that then can suppress hard coat descends.The preferred content of this silica granule based on the solids component weight of resin combination, is 3～20 weight %, is preferably 5～15 weight % especially.
The active energy ray-curable resin combination that uses among the present invention, as required, above-mentioned active energy ray-curable polymerizable compound, silica granule and Photoepolymerizationinitiater initiater that uses as required that can be by adding the defined ratio respectively in appropriate solvent or various added ingredients such as antioxidant, UV light absorber, photostabilizer, flow agent, defoamer etc. make its dissolving or dispersion and prepare.
As at this moment used solvent, can enumerate for example cellosolve kind solvents such as esters such as ketone such as alcohol, acetone, methyl ethyl ketone, 2 pentanone, isophorone, pimelinketone, ethyl acetate, butylacetate, ethyl cellosolves such as halohydrocarbon such as aromatic hydrocarbonss such as aliphatic hydrocarbon such as hexane, heptane, toluene, dimethylbenzene, methylene dichloride, ethylene dichloride, methyl alcohol, ethanol, propyl alcohol, butanols etc.
Concentration, viscosity as such composition prepared as long as can be coated with, have no particular limits it, can be suitably selected as required.
Then, by known method before above-mentioned composition is adopted for example rod be coated with method, scraper coating method (Na イ Off コ one ト method), rolling method, scraper plate coating method (Block レ one De コ one ト method), mould and be coated with method, photogravure coating method etc. and be coated with, its formation is filmed, after the drying, to its irradiation activation-energy-ray, make this curing of coating, thereby form hard coat.
As activation-energy-ray, can enumerate ultraviolet ray and electron beam etc.Above-mentioned ultraviolet ray can be by acquisitions such as high voltage mercury lamp, fusion H lamp, xenon lamps, and irradiation dose is generally 100～500mJ/cm
2, on the other hand, electron beam can be by acquisitions such as electron-beam accelerators, and irradiation dose is generally 150～350kV.In these activation-energy-rays, preferred especially ultraviolet ray.In addition, when using electron beam, can not add polymerization starter and obtain cured film.
The thickness of the hard coat of Xing Chenging is preferably the scope of 0.5～20 μ m like this.When this thickness less than 0.5 μ m, then there is the possibility of the scuff resistance that can not give full play to hard coat film, in addition if surpass 20 μ m, the possibility that then exists 60 ° of mirror surface lusters to increase.Consider that from the aspects such as harmony of scuff resistance and 60 ° of mirror surface lusters the preferred thickness of this hard coat is the scope of 1～15 μ m, is preferably the scope of 2～10 μ m especially.
The surperficial arithmetic average roughness Ra of the hard coat of Xing Chenging is generally 0.05～0.15 μ m like this, more preferably 0.05～0.10 μ m.Again, described arithmetic average roughness Ra is to be the value of benchmark mensuration with ISO 1997.
In addition, the hardness of this hard coat, preferred pencil hardness be H or more than, if pencil hardness be H or more than, then hard coat film can possess necessary scuff resistance, but if will make scuff resistance more abundant, then preferred especially pencil hardness be 2H or more than.
In addition, above-mentioned pencil hardness is according to JIS K 5400, scratches the value that method is measured by hand.
In anti-dazzle hardness film coating of the present invention, with 60 ° of mirror surface lusters of the turbidity value of JIS K 7136 regulation and JIS K 5600 regulations as anti-dazzle property index, turbidity value be preferably 2% or more than, and 60 ° of mirror surface lusters be preferably 150 or below.When turbidity value less than 2%, be difficult to bring into play sufficient anti-dazzle property, in addition, if 60 ° of mirror surface lusters surpass 150, then surface gloss very big (reflection of light is very big) becomes anti-dazzle property is caused dysgenic reason.But, if turbidity value is too high, light transmission variation then, thereby not preferred.In addition, anti-dazzle hardness film coating of the present invention represents that sharpness preferably has 100 or above value.So-called expression sharpness is to use the expression sharpness determinator of JIS K 7105 regulations among the present invention, use the 4 kind optical combs (optics く) of width as 0.125mm, 0.5mm, 1.0mm and 2.0mm, obtain sharpness (%) according to above-mentioned specification 6.6.4 and 6.6.5 by transmission method, these 4 numerical value are added up to the value of gained at each optical comb.This expression sharpness when this value less than 100, then can't obtain enough good demonstration image quality (visuality) as the index that shows that image quality is promptly visual.In addition, all light transmittances be preferably 90% or more than, when less than 90%, having then that the transparency is insufficient may.
From anti-dazzle property, show that the harmonious aspect of image quality (visuality), transmitance, the transparency etc. considers that turbidity value is preferably 3～80%, the expression sharpness more preferably 150 or more than, all optical transmittances more preferably 91% or more than.
In addition, the concrete measuring method for above-mentioned optical characteristics will describe in aftermentioned.
In the present invention, as required, on the surface of above-mentioned hard coat, can be provided with in order to give the antireflection layer of preventing property of reflection, type siloxane overlay film for example, fluorine class overlay film etc.At this moment, the thickness of this antireflection layer is more suitable about 0.05～1 μ m.In addition, the reflectivity of wavelength 550nm be preferably 3.5% or below.By this antireflection layer is set, can eliminate mirroring of the picture that produces by reflections such as sunlight, luminescent lamps, and, by suppressing surface albedo, can increase whole optical transmittances, enhance the transparency.In addition, according to the kind of antireflection layer, can reach the purpose that improves static resistance.
In anti-dazzle hardness film coating of the present invention, on the reverse side of the hard coat of base material film, can form and make it be attached to binder layer on the adherends such as liquid crystal display.As the tackiness agent that constitutes this binder layer, the tackiness agent that preferably uses optical applications to use, for example acrylic adhesives, urethanes tackiness agent, silicone tackiness agent.The thickness of this binder layer is generally 5～100 μ m, is preferably the scope of 10～60 μ m.
In addition, on this binder layer, as required stripping film can be set.As this stripping film, can enumerate for example stripping film of stripper such as coated silicone resin etc. on paper such as glassine paper, coated paper, laminated paper and various plastic film.Thickness to this stripping film has no particular limits, and is generally about 20～150 μ m.
Embodiment
Next, the present invention is carried out more specific description, be subjected to any qualification but the present invention can't help these embodiment by embodiment.
In addition, the size-grade distribution of silica granule and the performance of anti-dazzle hardness film coating are estimated according to following method.
(1) size-grade distribution of silica granule and median size
The laser diffraction and scattering formula particle size distribution device " LA-920 " that adopts (strain) hole field to make manufacturing is measured.
(2) whole light transmittances
According to JIS K 7361-1, " NDH2000 " that adopt Japanese electric look industry (strain) to make measures.
(3) turbidity value
According to JIS K 7136, " NDH2000 " that adopt Japanese electric look industry (strain) to make measures.
(4) 60 ° of mirror surface lusters
According to JIS K 5600, " VG 2000 " of adopting Japanese electric look industry (strain) to make are measured.
(5) expression sharpness
The expression tester " ICM-10P " that adopts ス ガ trier (strain) to make, according to JIS K 7105,6.6.4 and 6.6.5, obtain in 4 kinds of optical combs that width is 0.125mm, 0.5mm, 1.0mm and 2.0mm by transmission method and to represent sharpness (%), obtain by adding up to these 4 numerical value.
(6) surperficial arithmetic average roughness (Ra)
According to ISO 1997, " the SURFTEST SV-3000 " that adopt (strain) ミ Star ト ヨ to make measures.
(7) pencil hardness
According to JIS K 5400, the pencil cut hardness of film trier " NP-TYPE " that adopts the smart mechanism of (strain) Japan to do manufacturing is measured.
(8) scuff resistance
With hard coating surface friction back and forth on Steel Wool #0000 (loading 9.8N), confirm to have not damaged.
Embodiment 1
[waste river chemical industry (strain) is produced at 100 weight part uv curing resins, trade(brand)name " PVC one system セ Star ト 575CB ", solid component concentration 100%] in add 7 weight part surfaces [Fuji's シ リ シ ア chemistry (strain) produced through silica granule that organic surface treatment agent has been handled, trade(brand)name " サ イ リ シ ア 436 ", median size 4.1 μ m], gained material dispersion treatment in the ball mill that uses 2mm φ zirconium oxide bead was measured the size-grade distribution of silica granule after 90 minutes by the laser diffraction and scattering method.This size distribution is shown in Fig. 1, and simultaneously, the peak value and the specific surface area of median size, size-grade distribution are listed in table 1.
Then, this dispersion treatment thing is diluted with ethyl cellosolve, making the total solids constituent concentration is 40 weight %, preparation active energy ray-curable composition (coating agent).This coating agent is coated on the triacetyl cellulose class film that thickness is 80 μ m [Fuji's description Off イ Le system (strain) is made, trade(brand)name " T80UZ "] by マ イ ヤ one バ one No.8, after under 70 ℃ dry 1 minute, its irradiation 250mJ/cm
2The ultraviolet ray of irradiation dose makes its curing, forms hard coat.The thickness of this hard coat is 4.5 μ m.
The performance of gained hard coat film is listed in table 1.
In embodiment 1, except using " サ イ リ シ ア 456RC " [trade(brand)name, Fuji's シ リ シ ア chemistry (strain) is produced, median size 6.7 μ m] as the surface beyond the silica granule that organic surface treatment agent has been handled, make hard coat film similarly to Example 1.
The size-grade distribution of the silica granule of dispersion treatment is shown in Fig. 2, and simultaneously, the peak value and the specific surface area of median size, size-grade distribution are listed in table 1.In addition, the performance of hard coat film is listed in table 1.
Embodiment 3
In embodiment 1, except use " ニ Star プ シ one Le SS-50B " [trade(brand)name, eastern ソ one シ リ カ (strain) produces, median size 1.5 μ m] as the surface beyond the silica granule that organic surface treatment agent has been handled, make hard coat film similarly to Example 1.
The size-grade distribution of the silica granule of dispersion treatment is shown in Fig. 3, and simultaneously, the peak value and the specific surface area of median size, size-grade distribution are listed in table 1.In addition, the performance of hard coat film is listed in table 1.
In embodiment 1, as beyond the silica granule, make hard coat film similarly to Example 1 except using " ニ Star プ シ one Le E-200A " [trade(brand)name, eastern ソ one シ リ カ (strain) produces, median size 1.5 μ m].
The size-grade distribution of the silica granule of dispersion treatment is shown in Fig. 4, and simultaneously, the peak value and the specific surface area of median size, size-grade distribution are listed in table 1.In addition, the performance of hard coat film is listed in table 1.
Table 1
Comparative example 1
In embodiment 1, carry out making hard coat film similarly to Example 1 30 minutes silica granule dispersion treatment with 10000rpm except using dispersion machine [special machine chemical industry society make " T.K homodisperse machine "].
The size-grade distribution of the silica granule of dispersion treatment is shown in Fig. 5, and simultaneously, the peak value and the specific surface area of median size, size-grade distribution are listed in table 2.In addition, the performance of hard coat film is listed in table 2.
Comparative example 2
In embodiment 2, except the dispersion treatment of silica granule adopt carry out with the same dispersion machine of comparative example 1, make hard coat film similarly to Example 2.
The size-grade distribution of the silica granule of dispersion treatment is shown in Fig. 6, and simultaneously, the peak value and the specific surface area of median size, size-grade distribution are listed in table 2.In addition, the performance of hard coat film is listed in table 2.
Comparative example 3
In embodiment 3, except the dispersion treatment of silica granule adopt carry out with the same dispersion machine of comparative example 1, make hard coat film similarly to Example 3.
The size-grade distribution of the silica granule of dispersion treatment is shown in Fig. 7, and simultaneously, the peak value and the specific surface area of median size, size-grade distribution are listed in table 2.In addition, the performance of hard coat film is listed in table 2.
Comparative example 4
In embodiment 4, except the dispersion treatment of silica granule adopt carry out with the same dispersion machine of comparative example 1, make hard coat film similarly to Example 4.
The size-grade distribution of the silica granule of dispersion treatment is shown in Fig. 8, and simultaneously, the peak value and the specific surface area of median size, size-grade distribution are listed in table 2.In addition, the performance of hard coat film is listed in table 2.
Table 2
From table 1 and table 2, as can be seen, when the hard coat film among the embodiment is all keeping anti-dazzle property and have higher expression boldness, and has higher hardness.Though and the hard coat film in the comparative example all has higher hardness, represent that boldness is obviously lower, all light transmittance is also lower.
Anti-dazzle property film of the present invention is the surface hardness height not only, and is being used for various indicating meters, and during such as liquid-crystal display, plasma display, cathode tube even touch panel etc., visuality is also good when having anti-dazzle property.
Claims (7)
1. anti-dazzle hardness film coating, it is characterized in that on the one side at least of base material film, having by employing and contain the hard coat that cured article that the active energy ray-curable resin combination of silica granule forms forms, and the silica granule in the above-mentioned composition is a silica granule below the 4 μ m for particle diameter in the size-grade distribution of being measured by the laser diffraction and scattering method has peak value and median size respectively in the scope of 0.1～1 μ m and 1.5～5 μ m, and the specific surface area that this silica granule is measured by the laser diffraction and scattering method is 20000cm
2/ cm
3More than, the content of this silica granule is 1～20 weight % based on the solids component weight of above-mentioned composition.
2. the described anti-dazzle hardness film coating of claim 1, wherein the expression sharpness of anti-dazzle hardness film coating is more than 100.
3. claim 1 or 2 described anti-dazzle hardness film coatings, wherein contain by particle diameter in the size-grade distribution of laser diffraction and scattering method mensuration and in the scope of 0.1～1 μ m and 1.5～5 μ m, have peak value respectively, and median size is the active energy ray-curable resin combination of the following silica granule of 4 μ m, bigger by containing than above-mentioned silica granule median size, and the active energy ray-curable resin combination that has the silica granule of 1 peak value in the size-grade distribution of being measured by the laser diffraction and scattering method carries out grinding dispersion treatment by the machine with grinding dispersion function that utilizes shearing force, the median size that makes silica granule than grinding dispersion treatment before more than the little 0.5 μ m and make.
4. claim 1 or 2 described anti-dazzle hardness film coatings, wherein the arithmetic average roughness Ra of hard coat is 0.05～0.15 μ m.
5. the described anti-dazzle hardness film coating of claim 3, wherein the arithmetic average roughness Ra of hard coat is 0.05～0.15 μ m.
6. claim 1 or 2 described anti-dazzle hardness film coatings, wherein the thickness of hard coat is 0.5～20 μ m.
7. the described anti-dazzle hardness film coating of claim 3, wherein the thickness of hard coat is 0.5～20 μ m.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005035992 | 2005-02-14 | ||
| JP2005035992A JP4890770B2 (en) | 2005-02-14 | 2005-02-14 | Method for producing antiglare hard coat film |
| JP2005-035992 | 2005-02-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1831071A CN1831071A (en) | 2006-09-13 |
| CN1831071B true CN1831071B (en) | 2010-05-26 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2006100074640A Active CN1831071B (en) | 2005-02-14 | 2006-02-14 | Anti-dazzle hardness film coating |
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| Country | Link |
|---|---|
| JP (1) | JP4890770B2 (en) |
| KR (1) | KR101238616B1 (en) |
| CN (1) | CN1831071B (en) |
| TW (1) | TWI391251B (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008074945A (en) * | 2006-09-21 | 2008-04-03 | Aica Kogyo Co Ltd | Glare-proof hard-coating agent and glare-proof film |
| JP4944572B2 (en) * | 2006-10-31 | 2012-06-06 | リンテック株式会社 | Anti-glare hard coat film |
| JP2008119867A (en) * | 2006-11-09 | 2008-05-29 | Lintec Corp | Anti-glaring hard coat film |
| JP2008188989A (en) * | 2007-01-12 | 2008-08-21 | Sakai Silk Screen:Kk | Adhesion prevention sheet |
| JP5204706B2 (en) * | 2009-03-30 | 2013-06-05 | リンテック株式会社 | Method for producing Newton ring prevention film |
| JP5522720B2 (en) | 2009-10-07 | 2014-06-18 | 日東電工株式会社 | Antiglare hard coat film, polarizing plate and image display device using the same, and method for producing antiglare hard coat film |
| JP2012212119A (en) * | 2011-03-18 | 2012-11-01 | Sumitomo Chemical Co Ltd | Polarizer protective film |
| US9535280B2 (en) * | 2011-05-27 | 2017-01-03 | Corning Incorporated | Engineered antiglare surface to reduce display sparkle |
| CN103013219B (en) * | 2012-12-10 | 2014-07-16 | 合肥乐凯科技产业有限公司 | Curing resin composition for anti-dazzle hard coating and anti-dazzle hard coating |
| CN105839461B (en) * | 2012-12-20 | 2019-01-01 | 斯迪克新型材料（江苏）有限公司 | Adhesive tape cloudy surface anti-static coating |
| JP5690880B2 (en) * | 2013-07-04 | 2015-03-25 | リンテック株式会社 | Optical film |
| JP6205224B2 (en) * | 2013-09-25 | 2017-09-27 | 株式会社きもと | Base substrate sheet and capacitive touch panel |
| WO2016030738A1 (en) * | 2014-08-26 | 2016-03-03 | 王子ホールディングス株式会社 | Anti-glare laminate |
| JP6707811B2 (en) * | 2015-03-31 | 2020-06-10 | 大日本印刷株式会社 | Decorative sheets and materials |
| CN105566963A (en) * | 2015-12-25 | 2016-05-11 | 佛山佛塑科技集团股份有限公司 | Non-glare coating and non-glare membrane |
| CN107124900A (en) * | 2015-12-25 | 2017-09-01 | 松下知识产权经营株式会社 | Touch panel and display device using same |
| CN117098725A (en) * | 2021-03-30 | 2023-11-21 | 电化株式会社 | Inorganic powders, inorganic compositions and resin compositions |
| JP7657290B2 (en) * | 2021-03-30 | 2025-04-04 | デンカ株式会社 | Spherical inorganic powder and liquid sealing material |
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| CN1329644A (en) * | 1998-12-09 | 2002-01-02 | 日本化药株式会社 | Hard coating material and film obtained with the same |
| WO2004017105A1 (en) * | 2002-08-15 | 2004-02-26 | Fuji Photo Film Co., Ltd. | Antireflection film, polarizing plate and image display device |
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| JPH09251101A (en) * | 1996-03-15 | 1997-09-22 | Konica Corp | Protective film for polarizing plate |
| JPH11286083A (en) * | 1998-04-02 | 1999-10-19 | Oike Ind Co Ltd | Glare-proof film |
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| JP2002182015A (en) * | 2001-10-16 | 2002-06-26 | Dainippon Printing Co Ltd | Anti-glare film and method for producing the same |
| KR100467822B1 (en) * | 2002-02-15 | 2005-01-24 | 주식회사 엘지화학 | Coating composition for protecting dazzling effect |
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- 2006-02-06 KR KR1020060010951A patent/KR101238616B1/en active Active
- 2006-02-09 TW TW095104298A patent/TWI391251B/en active
- 2006-02-14 CN CN2006100074640A patent/CN1831071B/en active Active
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| CN1329644A (en) * | 1998-12-09 | 2002-01-02 | 日本化药株式会社 | Hard coating material and film obtained with the same |
| WO2004017105A1 (en) * | 2002-08-15 | 2004-02-26 | Fuji Photo Film Co., Ltd. | Antireflection film, polarizing plate and image display device |
| CN1503009A (en) * | 2002-11-20 | 2004-06-09 | 力特光电科技股份有限公司 | anti-glare film |
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| Publication number | Publication date |
|---|---|
| KR101238616B1 (en) | 2013-02-28 |
| JP2006218798A (en) | 2006-08-24 |
| CN1831071A (en) | 2006-09-13 |
| KR20060091233A (en) | 2006-08-18 |
| TW200702177A (en) | 2007-01-16 |
| JP4890770B2 (en) | 2012-03-07 |
| TWI391251B (en) | 2013-04-01 |
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